CN101481801B - Etching solution - Google Patents
Etching solution Download PDFInfo
- Publication number
- CN101481801B CN101481801B CN2008101857971A CN200810185797A CN101481801B CN 101481801 B CN101481801 B CN 101481801B CN 2008101857971 A CN2008101857971 A CN 2008101857971A CN 200810185797 A CN200810185797 A CN 200810185797A CN 101481801 B CN101481801 B CN 101481801B
- Authority
- CN
- China
- Prior art keywords
- group
- weight
- etching solution
- nickel
- polymkeric substance
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 238000005530 etching Methods 0.000 title claims abstract description 69
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 108
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 54
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 23
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 16
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 4
- 125000003118 aryl group Chemical group 0.000 claims abstract description 4
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 claims abstract description 4
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims abstract description 4
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims abstract description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 4
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims abstract description 4
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 claims abstract description 4
- 150000001412 amines Chemical class 0.000 claims abstract description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract 2
- 239000000126 substance Substances 0.000 claims description 34
- XLJMAIOERFSOGZ-UHFFFAOYSA-N cyanic acid Chemical compound OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- -1 amino, imino- Chemical class 0.000 claims description 4
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 21
- 229910052802 copper Inorganic materials 0.000 abstract description 20
- 239000010949 copper Substances 0.000 abstract description 20
- 239000002184 metal Substances 0.000 abstract description 17
- 229910052751 metal Inorganic materials 0.000 abstract description 17
- 239000007788 liquid Substances 0.000 abstract description 5
- 150000002739 metals Chemical class 0.000 abstract description 5
- 229920000642 polymer Polymers 0.000 abstract 2
- 150000003242 quaternary ammonium salts Chemical group 0.000 abstract 2
- 125000003277 amino group Chemical group 0.000 abstract 1
- 125000004093 cyano group Chemical group *C#N 0.000 abstract 1
- 125000000753 cycloalkyl group Chemical group 0.000 abstract 1
- 125000001841 imino group Chemical group [H]N=* 0.000 abstract 1
- 125000003396 thiol group Chemical group [H]S* 0.000 abstract 1
- 230000003628 erosive effect Effects 0.000 description 15
- 239000000203 mixture Substances 0.000 description 11
- 238000000034 method Methods 0.000 description 9
- 239000000178 monomer Substances 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- DYUWTXWIYMHBQS-UHFFFAOYSA-N n-prop-2-enylprop-2-en-1-amine Chemical compound C=CCNCC=C DYUWTXWIYMHBQS-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000013543 active substance Substances 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 210000000981 epithelium Anatomy 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- BZOVBIIWPDQIHF-UHFFFAOYSA-N 3-hydroxy-2-methylbenzenesulfonic acid Chemical compound CC1=C(O)C=CC=C1S(O)(=O)=O BZOVBIIWPDQIHF-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 229910000570 Cupronickel Inorganic materials 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- NJSSICCENMLTKO-HRCBOCMUSA-N [(1r,2s,4r,5r)-3-hydroxy-4-(4-methylphenyl)sulfonyloxy-6,8-dioxabicyclo[3.2.1]octan-2-yl] 4-methylbenzenesulfonate Chemical compound C1=CC(C)=CC=C1S(=O)(=O)O[C@H]1C(O)[C@@H](OS(=O)(=O)C=2C=CC(C)=CC=2)[C@@H]2OC[C@H]1O2 NJSSICCENMLTKO-HRCBOCMUSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- MMCPOSDMTGQNKG-UJZMCJRSSA-N aniline;hydrochloride Chemical compound Cl.N[14C]1=[14CH][14CH]=[14CH][14CH]=[14CH]1 MMCPOSDMTGQNKG-UJZMCJRSSA-N 0.000 description 1
- 150000008107 benzenesulfonic acids Chemical class 0.000 description 1
- CUBCNYWQJHBXIY-UHFFFAOYSA-N benzoic acid;2-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=CC=C1.OC(=O)C1=CC=CC=C1O CUBCNYWQJHBXIY-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 description 1
- 229960003280 cupric chloride Drugs 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- XWBDWHCCBGMXKG-UHFFFAOYSA-N ethanamine;hydron;chloride Chemical compound Cl.CCN XWBDWHCCBGMXKG-UHFFFAOYSA-N 0.000 description 1
- 239000011152 fibreglass Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- PJJJBBJSCAKJQF-UHFFFAOYSA-N guanidinium chloride Chemical compound [Cl-].NC(N)=[NH2+] PJJJBBJSCAKJQF-UHFFFAOYSA-N 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 150000003840 hydrochlorides Chemical class 0.000 description 1
- QWARLPGIFZKIQW-UHFFFAOYSA-N hydrogen peroxide;nitric acid Chemical compound OO.O[N+]([O-])=O QWARLPGIFZKIQW-UHFFFAOYSA-N 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 description 1
- 229940006461 iodide ion Drugs 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000004452 microanalysis Methods 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- HYEKBBUUXFWKKZ-UHFFFAOYSA-K sodium;zinc;trichloride Chemical compound [Na+].[Cl-].[Cl-].[Cl-].[Zn+2] HYEKBBUUXFWKKZ-UHFFFAOYSA-K 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/16—Acidic compositions
- C23F1/28—Acidic compositions for etching iron group metals
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K13/00—Etching, surface-brightening or pickling compositions
- C09K13/04—Etching, surface-brightening or pickling compositions containing an inorganic acid
- C09K13/06—Etching, surface-brightening or pickling compositions containing an inorganic acid with organic material
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/16—Acidic compositions
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Inorganic Chemistry (AREA)
- ing And Chemical Polishing (AREA)
- Weting (AREA)
- Manufacturing Of Printed Circuit Boards (AREA)
Abstract
The invention relates to an etching liquid, provides a nickel etching liquid which can inhibit the etching to metals except nickel, in particular copper. The etching liquid is a nickel etching liquid containing nitric acid or sulfuric acid, hydrogen peroxide and water, which is characterized in that it contains a polymer, and the polymer is selected from at least one repeating unit of the following formula (I), the following formula (II), and the following formula (III), wherein, R1-R5 are identical or different, are selected from hydrogen group, amino group, imino group, cyano group, azo group, mercapto group, sulfo group, hydroxyl group, carbonyl group, carboxyl group, nitro group, alkyl group, cycloalkyl group, aryl group or benzyl group, and amine contained in the repeating unit is in quaternary ammonium salt form or not in quaternary ammonium salt form.
Description
Technical field
The present invention relates to contain the etching solution of the nickel of nitric acid or sulfuric acid, hydrogen peroxide and water.
Background technology
Contain in the process of TAB (Tape Automated Bonding) with the electrode of electrode, wiring or the semiconductor article of the printed substrate of flexible base, board, BGA (BallGrid Array) base plate for packaging etc. in manufacturing, have through the operation of electroplating, electroless plating forms the nickel epithelium.At this moment, the nickel epithelium that forms in unwanted part is removed through etching solution.
Because former electrodes, wiring contain multiple metal, therefore when removing the nickel epithelium, require not corrode the metal except nickel.For example; Utilizing semi-additive process to make in the process of printed substrate, on the insulating substrate of woven fiber glass epoxy resin impregnation plate, polyimide film etc., carry out after chemical nickel plating, the vapor deposition nickel; Form the anti-pattern of circuit with resist; On the nickel that is not covered, form copper circuit, remove resist then, afterwards the nickel that exposes is carried out etching through electro-coppering by resist.For employed nickel etching solution this moment, require etching nickel under the situation that does not corrode copper circuit.
Remove the etching solution of nickel as not corroding copper, use the acid contain nitric acid etc. and the etching solution of hydrogen peroxide in the past always.In the etching solution of the nickel of these nitric acid-hydrogen peroxide system, be added with usually and be used to suppress erosive additive copper.(for example, with reference to patent documentation 1～8).
Patent documentation 1: special public clear 62-11070 communique
Patent documentation 2: special public clear 62-14034 communique
Patent documentation 3: special public clear 62-14035 communique
Patent documentation 4: the clear 58-500765 communique of special table
Patent documentation 5: the spy opens flat 6-57454 communique
Patent documentation 6: the spy opens flat 9-228075 communique
Patent documentation 7: the spy opens the 2001-140084 communique
Patent documentation 8: the spy opens the 2005-36256 communique
Summary of the invention
But even these etching solutions can not suppress the erosion to copper fully, the erosive nickel etching solution to copper appears further suppressing in expectation on market.
The objective of the invention is to, overcome technological deficiency in the past, the erosive nickel etching solution that can suppress metal, especially copper beyond the nickel is provided.
To achieve these goals; Etching solution of the present invention is the etching solution that contains the nickel of nitric acid or sulfuric acid, hydrogen peroxide and water; It is characterized in that, contain polymkeric substance, this polymkeric substance has at least one repeating unit in the following formula (I) that is selected from, following formula (II) and the following formula (III).
(wherein, R
1～R
5Identical or different; Be hydrogen, amino, imino-, cyanic acid, azo-group, sulfydryl, sulfo group, hydroxyl, carbonyl, carboxyl, nitro, alkyl, naphthenic base, aryl or benzyl, and contained amine is quaternary ammonium form or is not quaternary ammonium form in the said repeating unit.)
In addition, said etching solution of the present invention is the etching solution of nickel, but should " nickel " not only comprise pure nickel, also comprises nickelalloy.In addition, " copper " stated after also is same.Here, above-mentioned " alloy " is meant that for example containing major metal is the above metals of 50 weight %.
According to etching solution of the present invention, owing to contain polymkeric substance, this polymkeric substance has at least one repeating unit in the above-mentioned formula (I) that is selected from, above-mentioned formula (II) and the above-mentioned formula (III), therefore can suppress the erosion to the metal except nickel, especially copper.
Embodiment
Etching solution of the present invention is the etching solution that contains the nickel of nitric acid or sulfuric acid, hydrogen peroxide and water, it is characterized in that, contains polymkeric substance, and this polymkeric substance has at least one repeating unit in the above-mentioned formula (I) that is selected from, above-mentioned formula (II) and the above-mentioned formula (III).In the etching solution of the present invention, above-mentioned polymkeric substance is owing to become the erosion inhibitor of the metal beyond the nickel, thus can be from the treated material of nickel and other metals coexistences etching nickel optionally only.Especially, when above-mentioned other metals are copper, more effectively given play to the function of above-mentioned polymkeric substance as erosion inhibitor.
The sour composition of etching solution of the present invention is to dissolve by the composition of the nickel behind the hydrogen peroxide oxidation, as the high material of the solvability of nickel, uses nitric acid or sulfuric acid.In addition, sour composition also has the effect that promotes the nickel oxidation as secondary oxidizer.In these sour compositions, sulfuric acid is compared with nitric acid, but the effect of the little dissolving of the effect of dissolved copper nickel is also little.Therefore, from the viewpoint of activity duration, preferably use nitric acid as sour composition of the present invention.
The concentration of the sour composition in the above-mentioned etching solution is adjusted according to the dissolving tolerance of the nickel of etching speed, etching solution, but preferred 1.0 weight %～38.5 weight %, more preferably 3.0 weight %～27.0 weight %.When 1.0 weight % were above, etching speed was accelerated, and therefore can promptly carry out etching to nickel.In addition, the concentration through making sour composition can easily suppress the erosion to the metal (especially copper) beyond the nickel below 38.5 weight %.
The concentration of the hydrogen peroxide in the above-mentioned etching solution is adjusted according to the ability of removing of etching speed, nickel, but preferred 0.0175 weight %～17.5 weight %, more preferably 0.035 weight %～14.0 weight %, further preferred 0.35 weight %～7.0 weight %.When 0.0175 weight % is above,, therefore can promptly remove nickel because etching speed is accelerated.On the other hand, be below the 17.5 weight % through the concentration that makes hydrogen peroxide, can easily suppress erosion to the metal (especially copper) beyond the nickel.
In etching solution of the present invention, as erosion inhibitor, be combined with polymkeric substance, this polymkeric substance has at least one repeating unit in the above-mentioned formula (I) that is selected from, above-mentioned formula (II) and the above-mentioned formula (III).In addition; This polymkeric substance can be the multipolymer that is formed by at least one repeating unit and other the repeating unit that are selected from above-mentioned formula (I), above-mentioned formula (II) and the above-mentioned formula (III); Can also be the homopolymer that is formed by above-mentioned formula (I), above-mentioned formula (II) or above-mentioned formula (III), also can be by being selected from the multipolymer that the repeating unit more than 2 forms in above-mentioned formula (I), above-mentioned formula (II) and the above-mentioned formula (III).
Polymkeric substance with the repeating unit shown in the above-mentioned formula (I) for example can illustration use Epicholorohydrin as monomeric polycondensate, and kind is not special to be limited, and for example can from commercially available tensio-active agent, suitably select.Wherein, only want from the treated material of nickel and copper coexistence optionally etching nickel, then preferably have the polymkeric substance that utilizes the Epicholorohydrin and the repeating unit of nitrogen compound formation, especially preferably have the polymkeric substance of the repeating unit shown in the following formula (IV).
(wherein, R
6And R
7Identical or different, be hydrogen, amino, imino-, cyanic acid, azo-group, sulfydryl, sulfo group, hydroxyl, carbonyl, carboxyl, nitro, alkyl, naphthenic base, aryl or benzyl.And X
-Be cl ions, bromide anion, iodide ion, acetate ion or carbanion.)
Have the polymkeric substance of the repeating unit shown in the above-mentioned formula (IV) through use, can increase etching speed to nickel (below be called " ER1 ") and ratio (ER1/ER2) the etching speed of copper (below be called " ER2 ").Thus, can be from the treated material of nickel and copper coexistence etching nickel reliably only.As such polymkeric substance, can enumerate n n dimetylaniline/Epicholorohydrin polycondensate, n n dimetylaniline/ammonia/Epicholorohydrin polycondensate, hexanodioic acid/n n dimetylaniline/Epicholorohydrin/NSC 446 polycondensate etc.In addition, when using ammonia as monomer, the R in the repeating unit shown in the above-mentioned formula (IV)
6And R
7All be hydrogen.In addition, when using n n dimetylaniline as monomer, the R in the repeating unit shown in the above-mentioned formula (IV)
6And R
7All are methyl.
Polymkeric substance with the repeating unit shown in the above-mentioned formula (II) for example can illustration use NSC 20948 as monomeric polycondensate, and kind is not special to be limited, and for example can from commercially available tensio-active agent, suitably select.As concrete example, can enumerate the polycondensate that forms by the diallyl amine hydrochlorate, NSC 20948/acrylic acid polycondensate etc.In addition, when using NSC 20948 as monomer, the R in the repeating unit shown in the above-mentioned formula (II)
1Be hydrogen.
Polymkeric substance with the repeating unit shown in the above-mentioned formula (III) for example can illustration use Dyhard RU 100 as monomeric polycondensate, and kind is not special to be limited, and for example can from commercially available tensio-active agent, suitably select.As concrete example, can enumerate Dyhard RU 100/formaldehyde condensation products, Dyhard RU 100/NSC 446 polycondensate etc.In addition, when using Dyhard RU 100 as monomer, the R in the repeating unit shown in the above-mentioned formula (III)
2～R
5All be hydrogen.
The preferred 0.0001 weight % of the concentration of the above-mentioned polymkeric substance in the etching solution of the present invention～less than 3 weight %, more preferably 0.0005 weight %～1.5 weight %, further preferred 0.001 weight %～1.0 weight %.If in above-mentioned scope, then the erosion that suppresses under the etched degree of nickel the metal beyond the nickel can not hindered.
In whole repeating units of above-mentioned polymkeric substance, the shared ratio of at least one repeating unit that is selected from above-mentioned formula (I), above-mentioned formula (II) and the above-mentioned formula (III) is preferably 10～100 moles of %.This is owing to can more effectively suppress the erosion to the metal beyond the nickel.In addition; Aforementioned proportion (mole fraction) for example can utilize infrared analysis method (IR), elemental microanalysis method, liquid phase chromatography etc.; Obtain functional group contained in above-mentioned formula (I), above-mentioned formula (II) and the above-mentioned formula (III), the mole number of element-specific, and calculate by the relation of these values and number-average molecular weight.In addition, when the monomer composition was confirmed, monomer ratio just became mole fraction.Denominator when in addition, obtaining above-mentioned mole fraction is the total mole number of minimum repeating unit contained in the above-mentioned polymkeric substance.
The weight-average molecular weight of above-mentioned polymkeric substance is preferred 100～1,000,000, and more preferably 100～500,000.If in above-mentioned scope, then can not hinder under the deliquescent situation of above-mentioned polymkeric substance, more effectively suppress erosion to the metal beyond the nickel.
In the etching solution of the present invention, except mentioned component, under the degree that does not hinder effect of the present invention, can add other compositions.For example, as the stablizer of hydrogen peroxide, can add phenol such as Phenylsulfonic acid class, Whitfield's ointment such as cresol sulfonic acid.The concentration of these other compositions for example is about 0.01～5 weight %.
And then, for the erosion that promotes copper suppresses effect, can add chloride-ion source.As chloride-ion source, can illustration hydrochlorides such as hydrochloric acid, aniline hydrochloride, Guanidinium hydrochloride, ethylamine hydrochloride for example; The muriate of ammonium chloride, sodium-chlor, zinc chloride, iron(ic)chloride, cupric chloride, nickelous chloride etc. etc.The concentration of these chloride-ion source is in cl ions, normally about 1～60ppm.
Above-mentioned etching solution is dissolved in the water through making above-mentioned each composition, can easily prepare.As above-mentioned water, preferably removed the water of ionic substance, impurity, for example preferred ion exchanged water, pure water, ultrapure water etc.
Above-mentioned etching solution can be in use becomes the concentration of regulation with each components matching, also can the prepared beforehand liquid concentrator, and before using, dilute the back and use.The method of use of above-mentioned etching solution is not special to be limited.And the etching solution temperature during use is not special to be limited, but wants on suppressing the erosive basis of the metal beyond the nickel etching nickel more promptly, then preferably 20～50 ℃ of uses.
Embodiment
Below, the embodiment and the comparative example of the etching solution that the present invention relates to described.In addition, explanation of the present invention is not limited to following embodiment.
(polymkeric substance of A～J), each etching solution of forming shown in the preparation table 2 according to the measuring method shown in following, are estimated projects to use the kind shown in the table 1.Each etching solution at first is to make acid and hydroperoxide dissolution behind ion exchanged water, adds polymkeric substance and prepares.For the acid that cooperates, only embodiment 14 uses sulfuric acid, and other all use nitric acid.In addition, when the weight-average molecular weight shown in the table 1 is lower molecular weight (weight-average molecular weight: more than 50 and less than 50,000), use Gonotec manufactured steam pressure type apparatus for determination of molecular weight, at sample concentration 5 weight % (solvent: measure under condition toluene).In addition, HMW (weight-average molecular weight: in the time of 50,000～300,000), use the membrane type apparatus for determination of molecular weight of same manufactured, with above-mentioned same condition under measure.
< to the etching speed (ER1) of nickel >
Preparation is square with calendering nickel plate (high-purity chemical institute system) the cutting-out 4cm of thickness 1mm, and posts the test specimen that protective tapes forms at single face.Then, each the etching solution 100ml in the table 2 is added in the beaker, use tweezers that above-mentioned test specimen impregnated in each etching solution (25 ℃), in etching solution, test specimen is shaken (cycle: 2 seconds) in the limit in the horizontal direction, 1 minute etch processes is carried out on the limit.Then, by the weight of each test specimen before and after handling, utilize following formula to calculate ER1 (μ m/min).
ER1 (μ m/min)=(weight (g) after weight (the g)-processing before handling) ÷ test specimen area (m
2) density (g/cm of ÷ nickel
3) ÷ time of immersion (min)
< to the etching speed (ER2) of copper >
Preparation is square with Copper Foil (Furukawa Circuit Foil makes GTMP) the cutting-out 4cm of thickness 35 μ m, and posts the test specimen that protective tapes forms at single face.Then, each the etching solution 100ml in the table 2 is added in the beaker, use tweezers that above-mentioned test specimen impregnated in each etching solution (25 ℃), in etching solution, test specimen is shaken (cycle: 2 seconds) in the limit in the horizontal direction, 1 minute etch processes is carried out on the limit.Then, by the weight of each test specimen before and after handling, utilize following formula to calculate ER2 (μ m/min).
ER2 (μ m/min)=(weight (g) after weight (the g)-processing before handling) ÷ test specimen area (m
2) density (g/cm of ÷ copper
3) ÷ time of immersion (min)
In addition, for each etching solution, calculate the ratio (ER1/ER2) of above-mentioned ER1 and above-mentioned ER2.The ER1 of each etching solution, ER2 and their ratio (ER1/ER2) are shown in Table 2.
Table 1
| Kind | Change the method for examining *No. | CASNo. | Weight-average molecular weight | Monomer is formed (mol ratio) |
| A | - | - | 100,000～120,000 | Adipic acid/n n dimetylaniline/Epicholorohydrin/NSC 446 (1/1/1/1) |
| B | 7-(1518) | - | 280,000 | N n dimetylaniline/ammonia/Epicholorohydrin (1/1/2) |
| C | - | 26063-69-4 | 110,000 | The diallyl amine hydrochlorate |
| D | 7-(21) | - | 20,000～30,000 | Dyhard RU 100/NSC 446 (1/1) |
| E | 6-(1898) | - | 40,000 | NSC 20948/acrylic acid (1/1/1) |
| F | 6-(1429) | - | 40,000～80,000 | The dimethylaminoethyl methacrylate quaternary ammonium salt |
| G | 6-(1675) | 30551-89-4 | 60,000 | Diallyldimethylammonium chloride |
| H | 7-(741) | 9002-98-6 68130-97-2 | 70,000 | Ethylene imine |
| I | 7-(741) | 106899-94-9 | 300 | Ethylene imine |
| J | 7-(24) | - | 10,000～30,000 | N n dimetylaniline/Epicholorohydrin (1/1) |
The law of the regulation of the examination of * relevant chemical substance and manufacturing etc.
Table 2
As shown in table 2, according to embodiments of the invention 1～15, compare with comparative example 1～5, all can increase etching speed than (ER1/ER2).Can know from this result, according to the present invention, can be from the treated material of nickel and other metals (copper etc.) coexistence etching nickel optionally only.
Claims (5)
1. an etching solution is the etching solution that contains the nickel of nitric acid or sulfuric acid, hydrogen peroxide and water, it is characterized in that, contain polymkeric substance, this polymkeric substance has the repeating unit of following formula (III),
Wherein, R
2～R
5Identical or different; Be hydrogen, amino, imino-, cyanic acid, azo-group, sulfydryl, sulfo group, hydroxyl, carbonyl, carboxyl, nitro, alkyl, naphthenic base, aryl or benzyl, and contained amine is quaternary ammonium form or is not quaternary ammonium form in the said repeating unit.
2. etching solution according to claim 1, wherein, the content of said polymkeric substance is more than the 0.0001 weight %, and less than 3 weight %.
3. etching solution according to claim 1, wherein, in whole repeating units of said polymkeric substance, the shared ratio of the repeating unit of above-mentioned formula (III) is 10～100 moles of %.
4. etching solution according to claim 1, wherein, the weight-average molecular weight of said polymkeric substance is 100～1,000,000.
5. etching solution according to claim 1, wherein,
Said nitric acid or vitriolic concentration are 1.0 weight %～38.5 weight %,
The concentration of said hydrogen peroxide is 0.0175 weight %～17.5 weight %.
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2008004707 | 2008-01-11 | ||
| JP2008004707 | 2008-01-11 | ||
| JP2008-004707 | 2008-02-29 | ||
| JP2008262945A JP5360703B2 (en) | 2008-01-11 | 2008-10-09 | Etching solution |
| JP2008-262945 | 2008-10-09 | ||
| JP2008262945 | 2008-10-09 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101481801A CN101481801A (en) | 2009-07-15 |
| CN101481801B true CN101481801B (en) | 2012-09-26 |
Family
ID=40879087
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008101857971A Expired - Fee Related CN101481801B (en) | 2008-01-11 | 2008-12-10 | Etching solution |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP5360703B2 (en) |
| KR (1) | KR101462286B1 (en) |
| CN (1) | CN101481801B (en) |
| TW (1) | TWI464301B (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102230178B (en) * | 2011-04-29 | 2012-09-05 | 西安东旺精细化学有限公司 | Etching liquid composition for nickel or nickel/copper alloy |
| KR101298766B1 (en) * | 2011-05-20 | 2013-08-21 | 주식회사 익스톨 | Etching solution composites for nickel, chrome, and/or nickel-chrome alloy and etching method using the etching solution composites |
| CN103281863B (en) * | 2013-04-28 | 2016-04-20 | 胜宏科技（惠州）股份有限公司 | The reworking method of the gold-plated finger of a kind of wiring board |
| KR101590258B1 (en) * | 2014-07-04 | 2016-02-01 | 오씨아이 주식회사 | Etching composition for metal layer comprising nickel |
| CN105506628B (en) * | 2015-12-03 | 2018-01-12 | 苏州鑫德杰电子有限公司 | A kind of compatibile extract etching solution and preparation method thereof |
| JP6471140B2 (en) * | 2016-11-30 | 2019-02-13 | 福田金属箔粉工業株式会社 | Composite metal foil, copper-clad laminate using the composite metal foil, and method for producing the copper-clad laminate |
| CN107740101A (en) * | 2017-09-19 | 2018-02-27 | 合肥惠科金扬科技有限公司 | A kind of etching solution for AMOLED array basal plate copper conductor |
| CN108754498A (en) * | 2018-06-15 | 2018-11-06 | 西安微电子技术研究所 | A kind of method that cryochemistry nickel groove body deposited nickel layer takes off except solution and take off nickel layer |
| CN113957442A (en) * | 2021-02-01 | 2022-01-21 | 江苏悦锌达新材料有限公司 | Nickel removing liquid medicine for nickel electroplating anti-corrosion layer, preparation method and chemical nickel removing process |
| CN113773840B (en) * | 2021-08-13 | 2022-08-02 | 晶瑞电子材料股份有限公司 | Etching solution and preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1180459C (en) * | 1997-11-21 | 2004-12-15 | 国际商业机器公司 | Etching composition and use thereof |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3540887B2 (en) * | 1996-02-26 | 2004-07-07 | 荏原ユージライト株式会社 | Selective nickel stripping solution and stripping method using the same |
| JP4241018B2 (en) * | 2002-12-06 | 2009-03-18 | メック株式会社 | Etching solution |
| US7176041B2 (en) * | 2003-07-01 | 2007-02-13 | Samsung Electronics Co., Ltd. | PAA-based etchant, methods of using same, and resultant structures |
| KR101230817B1 (en) * | 2004-12-13 | 2013-02-07 | 동우 화인켐 주식회사 | ETCHANT COMPOSITION FOR Al-Ni-metal ALLOY LAYER |
| JP2007180172A (en) * | 2005-12-27 | 2007-07-12 | Mec Kk | Manufacturing method of board |
-
2008
- 2008-10-09 JP JP2008262945A patent/JP5360703B2/en active Active
- 2008-11-17 TW TW097144320A patent/TWI464301B/en active
- 2008-12-10 CN CN2008101857971A patent/CN101481801B/en not_active Expired - Fee Related
-
2009
- 2009-01-09 KR KR1020090001887A patent/KR101462286B1/en active IP Right Grant
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1180459C (en) * | 1997-11-21 | 2004-12-15 | 国际商业机器公司 | Etching composition and use thereof |
Non-Patent Citations (1)
| Title |
|---|
| JP平9-228075A 1997.09.02 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101481801A (en) | 2009-07-15 |
| TW200930839A (en) | 2009-07-16 |
| JP2009185377A (en) | 2009-08-20 |
| KR20090077718A (en) | 2009-07-15 |
| JP5360703B2 (en) | 2013-12-04 |
| KR101462286B1 (en) | 2014-11-14 |
| TWI464301B (en) | 2014-12-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101481801B (en) | Etching solution | |
| JP4932094B2 (en) | Electroless gold plating solution and electroless gold plating method | |
| JP4116718B2 (en) | Electroless gold plating method and electroless gold plating solution used therefor | |
| CN1819748B (en) | Etching liquid, bulking liquid and forming method of conductive image using same | |
| TWI682064B (en) | Plating bath composition and method for electroless plating of palladium | |
| JP2001140084A (en) | Etching solution for nickel or nickel alloy | |
| CN112048718A (en) | Compositions and methods for microetching copper and copper alloys | |
| EP3049549B1 (en) | Method for treatment of recessed structures in dielectric materials for smear removal | |
| US20230220558A1 (en) | An aqueous basic etching composition for the treatment of surfaces of metal substrates | |
| US20180179633A1 (en) | Electroless plating method | |
| JP3235248B2 (en) | Stripping method and stripping solution for water-soluble resist | |
| JP6715246B2 (en) | Displacement preventive agent for electrolytic hard gold plating solution and electrolytic hard gold plating solution containing the same | |
| CN115291483B (en) | Semiconductor stripping liquid and preparation method thereof | |
| CN116601331A (en) | Etchant and method for manufacturing circuit board | |
| JP3421333B2 (en) | Stripping method and stripping solution for water-soluble resist | |
| CN115715487A (en) | Method for manufacturing printed wiring board | |
| US20180179634A1 (en) | Method for electroless plating | |
| JP2022184639A (en) | copper etchant |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20120926 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |